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HIGHLIGHTS ON THE LATEST BATTERY TECHNOLOGY ACHIEVEMENTS & CHALLENGES
CEA tech - LITEN | PATOUX Sébastien
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The world’s most innovative research
institutions (Rank #1 in 2016 ; #2 in 2017)
CEA in brief: Technological strength-in-depthfrom atomic research to renewable energy
17 000 employees10 Research centers4B€ annual budget
700 priority patents filed / P.A.120 new high-tech start-up /companies created since 1984
639 patents /year (2016)
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Liten covers the entire value chain from materials to systems
MATERIALS
PROCESSES
COMPONENTS
SYSTEM INTEGRATION
DEMONSTRATION
FIRST PROTOTYPES
Impossible d’afficher l’image.
X rays Nanotomographyof ceramic cells
X rays Nanotomographyof ceramic cells
Powder for batteries
Powder for batteries
Fuel cell catalystFuel cell catalyst
Atomic scale modelling of
hybrides
Atomic scale modelling of
hybrides
Solar cellsSolar cellsBatteries cellsBatteries cells
PEMFC systemPEMFC system
Alsolen: 500 KW Fresnel Concentrated Solar Power Alsolen: 500 KW Fresnel Concentrated Solar Power
Integration of CEA technologies 15 KWh Li Battery + 25 kW PEMFC + 10,5 kg H2 ~350 kWh
Integration of CEA technologies 15 KWh Li Battery + 25 kW PEMFC + 10,5 kg H2 ~350 kWh
Solar charging station and micro gridSolar charging station and micro grid
Data analysis, modeling & simulationData analysis, modeling & simulation
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SMART GRIDTHERMAL SYSTEMS
POWDER METALLURGY
MICRO SOURCESLARGE SURFACE PRINTED
ELECTRONICS
NANO CHARACTERISATION
FUEL CELLS SOLAR PHOTOVOLTAICS
BIOMASS BATTERIESHYDROGEN
ELECTRIC VEHICLESBUILDING
Liten Institute Technology Platforms
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Material synthesis. Electrode coating. Cell andpack assembly. Mechanical and Electricaldesign. BMS architecture, Thermal modelling.Characterization. Abuse tolerance testing.
200 engineers and technicians ; >350 patents
5000 m² space (incl. 1000 m² of anhydrous labs)
60M€ investment since 2010
Industrial partners in France, Europe, Japan,Korea, US and Bolivia.
Focusing on lithium-ion battery development, the
platform develops end-to-end production systems for
wide-ranging applications. Unique in Europe, the
platform helps industry boost battery life, improve
reliability and cut costs.
BATTERY PLATFORM
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Characterization
& modeling
Electrodes
Components
Cells
Modules/packs
LCA/Recycling
OUR POSITIONNING
Abuse testing
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For more than 20 years !
MATERIALS SYNTHESIS : from g to Kg
- Organic materials
- Organic materials
- Water-based electrolyte (Li or Na ions)
- Paper-based separator
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Lab coater
(doctor blade)
L= 30 cm, l = 10 cm
Pre-pilot scale
(comma-bar)
L= 10 m, l = 14 cm
Pilot-scale
COATEMA (slot die)
L= 80 m, l = 200 mm
Pre-industrial scale
MEGTEC (slot die)
ELECTRODE COATING (including water-based and
solvent-free solutions)
10 – 250 mLThree-roll mill
High-shear disperser + ink ball-milling60 L
• COATING
• SLURRY PREPARATION
L= 300 m, l = 600 mm
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CELL ASSEMBLY AND TESTINGDry room ~ 1000 m²
Channels up to 700 V, 1000 A, 250 kW
- A stabilized design to investigate new chemistries,
- Capability to assemble prototypes in small series
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Electromobility application batteryPowerful and durableThe battery that gives the autonomy you need for your journey
Sensor batterySmall and resistantThe battery suitable for extreme external environments
Safety beacons batteryLong-life and reliableThe battery that ensures reliable communication everywhere
Medical ImplantSmall, safe & biocompatibleThe battery you can rely on for 10 years at body temperature
Ultra-thin batteryLight and discreteUltra light and ultra compact
Primary batteryLow-cost and storableThe battery that meets your short-time and sporadic energy needs
…and more
18650 standardFor representative benchmarkIndustrial reference
From 1 mAh to 70 Ah Li-ion cells, with on-demand packaging, architectures and designs
BATTERY CELL CUSTOMIZATION
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BATTERY DEVELOPMENT (MECHANIC, ELECTRIC AND
THERMAL DESIGNS)
- Battery Modules & pack assembly with e-management
- Semi automatic assembly with full components tracking
From kWh to MWh
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MODULE & PACKS – VARIOUS EXAMPLES
PHEV: HYPACK modules 7 kWh 400 V
E-bike: MOBILAB module
6 Ah 36 V
Fast charging e-Bus: MC2
module 70 kWh 700 VE-Boat ZERO CO2 PACK
16 kWh 400 V
EV: RC2 module 12 kWh 400 V
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EXPERIMENTATION with CEA battery system inside
End of bus line charge = 250kW in 5 min
27 kWh – 160 Wh/kg battery pack2 x 45 kWh battery packs
EOLAB hybrid concept car (7kWh,1L/100km)
Full Elec Power Pack (3 x 85 kWh)
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PV, controllable load banks, 45 kW grid
simulator, and battery emulators
EV charging station
Storage systems
(Batteries, H2, hybrid)
Houses
Energy software
intelligence
Smart micro-grid250kVA
80 kW PV and diesel
genset power production
Heat
microgrid
DEMONSTRATION IN SMART GRID
Technology selection & management optimization
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Lithium-sulfur Sodium-ion Hybrid
SupercapacitorsNickel-zinc
Increase performances
• Energy
• Power
Decrease costs
• Economical
• Environmental
• Risks
Widen operational
conditions
• Temperature
• Flexibility• Durability
Metal-air
BEYOND conventional Li-ion batteries
Mg- and
Al-ion
Solid electrolytesOrganic Flexible Printed Composite
packagingRedox Flow
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TOWARDS LOW COST AND GREEN BATTERIES
� High and tunable electrochemical performancesPower : C-rate above 150C (charge in few seconds)
Energy : energy density x 2 (multi-redox reaction)
Tunable redox potential (chemical environment)
Various counter ions (Li+, Na+, K+, Mg2+,…)
� Low cost and sustainable electrode materialsLow cost precursors (biomass) / Green chemistry
Biodegradable / Recyclable
Less toxic (?)
Our building block : C,H, O, N, (S)
Cycle life of a ‘‘greener’’ Li-ion battery
based on organic materials
Poizot, Energy Env. Sci, 2011
Main issues :� Low electronic conductivity� Low cyclability (solubility in
electrolytes)
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EXAMPLE OF FULL ORGANIC BATTERY
Synthesis of positive and negative organic materials at pilot scale
Assembling full organic battery
� 1.2 V battery wih good cycle life. To be continued…
Iordache A., Delhorbe V., Bardet, M., Dubois L., Gutel T., Picard L. Appl. Mater. Interfaces , 2016
• Flexible
• Printed
• Colored
• Redox Flow
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POSITIONNING OF THE BATTERY TECHNOLOGIES
SAFETY
POWER
ENERGY
Supercapacitors
Li-Sulfur
Today’sLi-ion
ImprovedLi-ion
High Power Li-ion
KIC
Na-ion
Towards Solid State Batteries
Cycle life
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• Li-rich* materials : one of the best solution for cathode**
• Silicon based materials : the best solution for anode
• Li-metal anode should also beconsidered again
Li-rich/Si-C
Li-rich/Li
* Li-rich = Li1+xM1-xO2 (0<x<1/3 ; M = Mn, Ni,…)**New HEC (rocksalt…) are also investigated at CEA
HIGH ENERGY Li-ION BATTERIES
Silicon anodeLi-rich (Ni-rich) cathode
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High Energy Li-on roadmap
• Li-rich* materials : one of the best solution for cathode**
• Silicon based materials : the best solution for anode
• Li-metal anode should also beconsidered again
Li-rich/Si-C integration
Cell energy : 300Whkg-1
Configuration : 5S4P
Battery capacity : 16Ah
Battery voltage : 17V
Device rate : 8A (C/2)
Li-rich/Si-C
Li-rich/Li
* Li-rich = Li1+xM1-xO2 (0<x<1/3 ; M = Mn, Ni,…)**New HEC (rocksalt…) are also investigated at CEA
HIGH ENERGY Li-ION BATTERIES
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FROM LIQUID ELECTROLYTES…
• Ionic liquids• New solvents• Additives
• High flash point• Ionic liquids• Aqueous electrolyte• Redox shuttle• HF Scavenging• No gas generation
• New solvents• Additives• SEI promoting agents
• Low viscosity• High ionic conductivity• Aqueous electrolytes
HIGH POWER
HIGH VOLTAGE
HIGH T°C
LOW T°CSAFETY
+ Good wettability+ No metal dissolution
+ No current collector corrosion
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TO GELIFIED ELECTROLYTES
PCE (Lithium salt in succinonitrile)
� Alternative non-flammable electrolyte solvent
� Good ionic conductivity with 1M LiTFSi � 3.10-3 S/cm (RT)
� Operating temperature -20°C�150°C
� Non volatile � boiling point 266°C
� Low cost
� Good electrochemical stability (up to 5.5V)
Plastic Crystal based Electrolyte
Room T°C Room T°C
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AND SOLID STATE ELECTROLYTES
Inorganic Crystalline Materials(Perovskites, Garnets, Nasicon)
Inorganic Amorphous Materials(LiPON, glass sulfides…)
Solid polymers
with additives
to improve
Conductivity
(various options)
• 3 types of solid electrolytes :
� Eliminate flammable & toxic liquid electrolyte � Develop solid electrolyte
cathode
anode
� Low conductivity, high interface
resistance, processability issue at
the moment, but…
� Safer batteries and Higher
energy density expected :
• Less safety control embedded
• Unlock Li-metal anode
� New architecture, new processes
Understanding & fine characterizations (HRTEM, EELS, TOF-SIMS, 3D-FIB-SEM…)
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Sulfur cathode : 1675 mAh/gLi-ion : 100-250 mAh/g
Lithium anode : 3860 mAh/gLi-ion : 372 mAh/g
Li-S nominal voltage : 2.2 VLi-ion : 3.3 – 3.7 V
Material properties
• Liquid through solid electrolyte
• High energy in lightweight batteries
• Low cost and low environmental impact
Challenges
� Sulfur dissolution
� Polysulfide dissolution� � Changes in positive electrode morphology,
pulverization� � Polysulfide shuttle
Nucleophilic polysulfides� Restricted electrolyte choice
Lithium metal corrosion (electrolyte, Li2Sn)
� Lithium cyclability, foam, dendrites
� Insulating and insoluble Li2S/S8� Electrode passivation� High carbon content
LITHIUM/SULFUR BATTERIES
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Sulfur cathode : 1675 mAh/gLi-ion : 100-250 mAh/g
Lithium anode : 3860 mAh/gLi-ion : 372 mAh/g
Li-S nominal voltage : 2.2 VLi-ion : 3.3 – 3.7 V
Material properties
Li/S roadmapSeveral strategies
+ + =
First cylindrical hard packaging cells (AA design)
• A compromise
between Energy and
Cycle life.
• Not so good in Wh/L
LITHIUM/SULFUR BATTERIES
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NA-ION : AN ALTERNATIVE TO THE
LI-ION TECHNOLOGY ?
• Design and development of new materials for Na-ion
• Material scale-up (kg)
• « Product » approach (↗ TRL)
• Battery Platform with control of the whole value chain
The 6th most abundantelement in the Earth Crust(33th for Lithium)
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NA-ION : AN ALTERNATIVE TO THE
LI-ION TECHNOLOGY ?
24 cells 50125, 960Wh, 48V
► High performances in terms
of Power & Cycle life.
► Ready for making the first
demonstrators (module & pack)
Backup stationary application
(UPS).
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HYBRID STORAGE SYSTEM : LI-ION CAPACITOR
Li-ion capacitor
++++++++
-
-
-
-
-
-
e-
+-Li+
Li+
Li+Li+
Li+Li+
Li-ion battery EDLCLIC
Graphite Activatedcarbon
EDLC
Li-ion battery
Pack power density
Pack energydensity
Cycleability(>5000 @ 100%DoD
Cost(TCO vs cycle)
Low T (<-10°C)
Safety
++++++++
--------
-
-
-
-
-
-Activatedcarbon
Activatedcarbon
+
+
+
+
+
+
+-
Graphite Insertion material
+-e-
Li+ Li+
Li+Li+
Li+
Li+
Li+Li+
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0 50 100 150 200 250 300 3500,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
0 20 40 60 80 100 120140 160 1800,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
Umax = 1,75V
Umax = 3,5V
U (
V)
time (h)
Umax/2 = 1,35V
U (
V)
time (h)
Umax = 2,7V
Cost efficiency
Improvement of device safety
POTASSIUM-ION CAPACITOR SYSTEM (KIC)Key point of the technology
Presence of potassium
Aluminum current collector
Compatibility with acetonitrile
++++++++
PF6-
K+ K+
K+ K+
K+ K+
Graphite /KPF6 1M (ACN)/Activated carbon
No signature of SEI formation
No risk of potassium plating
PF6-
PF6-
Hybrid KiC
Conventional EDLC
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KIC FULL CELL TESTING
Device ageing at RT High rate performances
Excellent stability at high charge/discharge rate (>100,000 cycles)
Excellent performances at high rates (95% retention at 300D; 86% at 400D)
Low heat elevation (+1°C at 400D)
7.4 Wh.kg-1 and 3.4 kW.kg-1 in 18650 cell
Prelimirary results ; improvement on going (patents filling)
Vol
tage
(V
)
Cell capacity (mAh)
18650 cell
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MAIN TARGETS
• New materials for anode, cathode,
electrolyte, packaging,…
• New processes (printing, extrusion, RTM,
flame spray or laser pyrolysis…)
• Solid state batteries (safety)
• Lithium metal control (structuration and
protection)
• New architectures (3D, conformable,…)
• Various battery technologies
• Hybridation with fuel cells, solar panels,
wind turbines…
Commissariat à l’énergie atomique et aux énergies alternatives
Centre de Grenoble | 38054 GRENOBLE Cedex 09
T. +33 (0)4 38 78 29 20 | [email protected]
Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019
Direction de la Recherche TechnologiqueLiten
Thank youfor your
attention !
Contact : [email protected]